Journal of Electroanalytical Chemistry 882 (2021) 115005

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Journal of Electroanalytical Chemistry

journal homepage: www.elsevier.com/locate/jelechem

Confined pulverization promoting durable pseudocapacitance for

FeOOH@PEDOT anode in Li-ion battery
⁎
Hui Qi a, Jianfeng Huang b, , Lin Tang a, Meng Ma b, Wen Deng a, Changfu Zhang a,
⁎
a
Xi'an Technological University, Xi'an, Shaanxi 710021, China
b
Shaanxi University of Science & Technology, Xi'an, Shaanxi 710021, China

A R T I C L E I N F O A B S T R A C T

Article history: β-FeO1-xOHClx (β-FeOOH) with 2 × 2 tunnel structure and high theoretical capacity over 1000 mAh g−1, is a potential
Received 15 November 2020 candidate for fast charging anodes for Li-ion batteries. However, low electrical conductivity and poor structure stabil-
Received in revised form 26 December 2020 ity leading to inferior rate performance and short life span restrict its further application. In this paper, conductive poly
Accepted 10 January 2021
(3,4-ethylenedioxythiophene) (PEDOT) polymer supported and coated FeOOH rods (FeOOH@PEDOT) was synthe-
Available online 12 January 2021
sized by a facile one-pot fmethod. Lots of nanopieces with abundant active sites were formed during conversion reac-
Keywords:
tion. The coating structure of FeOOH@PEDOT provided closer electrical contact for the pulverized FeOOH particles.
FeOOH Therefore, the confined pulverized particles with high surface area and good electrical conductivity adopt fast
PEDOT pseudocapacitive reaction kinetics to realize high rate performance. Consequently, FeOOH@PEDOT composites as
Pseudocapacitance Li ion anodes exhibit extended cycle life and enhanced rate capability. This work reveals that conductive polymer con-
Pulverization fined pulverization process could realize fast and durable storage for converse-type anodes.
Li-ion batteries

1. Introduction
Lithium ion batteries have been widely applied into portable devices
and large electric vehicles owing to its light weight and high energy density.
Developing anodes with high power density would be the key for next-
generation of lithium ion batteries. Iron based anodes have attracted in-
creasing attention due to low cost and environmental benignity [1,2]. β-
FeOOH, as a member of FeOOH polymorphs, is one of the promising anodes
owing to its high theoretical capacity of 746.1 mAh g−1 with unique 2 × 2
tunnel structure located with Cl−, shown as β-FeO1-xOHClx [3–6]. Due to
the unique structure and composition, β-FeOOH have been widely applied
as anode material for Lithium-ion batteries.
However, its low electrical conductivity and structure instability lead to
inferior rate performance and poor cycling durability, which restricts its
further application in Li-ion batteries. To surmount these problems, mas-
sive efforts have been dedicated to improving electrical conductivity and
structure integrity, including tailoring active materials into nano sizes and
introducing high conductivity materials such as graphene and carbon nano-
tubes (CNTs) [7–10]. For example, Yu reported bunched β-FeOOH nanorod
arrays on carbon cloth (CC/β-FeOOH), which exhibits high rate ability but
short cycling life with 150 cycles [11]. In our previous work, FeOOH ar-
rays/RGO were fabricated and shows fast charge transfer and high struc-
ture stability due to the abundant Fe-O-C bonds between FeOOH rods and
RGO substrates. In addition, we found converse-type anode materials
would pulverize into nano pieces during repeated expansion and extraction
[12]. The nano pieces possess high surface area, which could provide more
active sites for redox reaction and accelerate ion transfer rate. The main
issue is how to keep electron contact between pulverized nano pieces.
Through building Fe-O-C bonds between the pulverized particles and
RGO (reduced graphene oxides) sheets, fast charging with
pseudocapacitive mechanism could be realized. Therefore, pulverization
induced reducing size for active materials could improve the rate perfor-
mance for FeOOH to some extent. However, pulverization also brings
about structure instability. Chemical bonds could only keep the electrical
contact for a short time since that FeOOH belongs to converse-type anode
material, which undergoes complete phase change and significant volume
variation during charge/discharge process [4]. Compared with insertion-
type anodes, converse-type materials witness more vigorous volume expan-
sion and extraction [13]. The simple structure of FeOOH/carbon hybrids
with anchoring FeOOH particles on carbon surfaces provides incomplete
protection of the active conversion-type materials and finally lost electrical
contact with each other. Therefore, FeOOH/carbon hybrids with simple an-
choring structure need further improvement for electrode stability.
Recently, confining the active material into fixed carbon shell with high
mechanical strength is confirmed to be one of most effective solutions for
the converse-type anodes [14–16]. The carbon shell could prevent the pul-
verized particles from losing effective electrical contact to ensure stable
cyclability [17]. However, carbon coating is not suitable for FeOOH since

⁎ Corresponding authors.
E-mail addresses: huangjf@sust.edu.cn (J. Huang), cfzhang@xatu.edu.cn (C. Zhang).

http://dx.doi.org/10.1016/j.jelechem.2021.115005
1572-6657/© 2021 Elsevier B.V. All rights reserved.
H. Qi et al.
FeOOH will transform into Fe2O3 when carbonization temperature is
higher than 150 °C. Thus, conductive polymer coating provides a good
choice for FeOOH [18–20]. The poly(2,3-dihydrothieno-1,4-dioxin)
(PEDOT) is a kind of highly conductive polymer, which could be polymer-
ized under 50 °C. Moreover, PEDOT is more flexible than hard carbon coat-
ing, which could tolerate severer volume expansion/contraction. For
example, uang introduced PEDOT layer to the surface of nickel sulfide ar-
rays to obtain durable cathode material for asymmetric supercapacitor
[21]. Jiang used in situ polymerization method to synthesize MnHCF@
PEDOT with ultra-long cycle life (1000 cycles with 78.3% capacity reten-
tion) [22]. Therefore, it would be an effective way to prolong cycle life
through constructing PEDOT coating on the surface on FeOOH.
In this work, flexible PEDOT polymer coated and supported β-FeOOH
rods (β-FeOOH@PEDOT) were successfully constructed and employed as
anodes for Li ion batteries. Compared with FeOOH rods anchoring RGO
substrates (β-FeOOH/RGO), the shell-core structure could provide closer
electrical contact for the pulverized particles. Benefiting from high surface
area of pulverized particles, FeOOH@PEDOT have fast pseudocapacitive
reaction kinetics to realize high rate performance. In addition, the flexible
PEDOT shell guarantees high structure integrity to extend cycle life of
FeOOH@PEDOT. In contrast, pulverized FeOOH particles in FeOOH/RGO
finally lose electrochemical activity due to lack of electrical contact. Conse-
quently, FeOOH@PEDOT composites as Li ion anodes exhibit extended
cycle life and enhanced capacity retention. The confined pulverization
boosted pseudocapacitive mechanism was also discussed. This work dem-
onstrates that it is significant to improve electrical conductivity of pulver-
ized particles to make best use of pulverization of converse-type anodes
to realize fast and durable storage (Scheme 1).
2. Experimental section
2.1. Preparation of β-FeO1-xOHClx@PEDOT (β-FeOOH@PEDOT)
In a typical procedure, 0.142 g 3,4-ethylenedioxythiophene (EDOT)
(1 mmol) and 0.011 g CTAB (0.3 mmol), 0.8 mg PAA and 0.81 g FeCl3∙
6H2O (3 mmol) were added into 40 mL deionized water to form aqueous
solution after magnetic stirring for 1 h. The obtained mixture was kept
under 50 °C for 48 h without stirring. The final black precipitates were
Scheme 1. Structure evolution resulted reaction kinetics for FeOOH/RGO and FeOOH@PEDOT under charge/discharge process.
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Journal of Electroanalytical Chemistry 882 (2021) 115005
washed with deionized water for several times and then frozen dried for
24 h.
2.2. Preparation of β-FeOOH/RGO and pure β-FeOOH
In a typical procedure, 30 mg of GO was distributed in 40 mL deionized
water for 2 h sonication to form a suspension. And then 0.81 g FeCl3∙6H2O
(3 mmol) were added into the above suspension for continuous 2 h of stir-
ring. Then put the mixture into Teflon-lined autoclave to maintain at 100 °C
for 6 h. The final products were washed by deionized water for several
times and then frozen dried for 24 h. The fabrication of pure β-FeOOH is
similar with that of β-FeOOH/RGO without addition of GO.
2.3. Materials characterization
The crystalline phase of samples was examined by XRD (Ultima IV) with
Cu Kα radiation. Morphology and microstructure were observed by FESEM
(Hitachi, S-4800) and TEM (FEI Tecnai G20, 200 kV). FITR (Bruker Vector-
22) were employed to analyze the organic groups of PEDOT to ensure the
existance of PEDOT.
2.4. Electrochemical measurements
The electrochemical properties of obtained samples were tested by half
cell. The fabrication of cell including the stages of slurrying, filming and as-
sembling. The ingredients of slurry include active materials, conductive
carbon (Super P) and binders (carboxymethyl cellulose, CMC) with mass
ratio of 8:1:1. Put the ingredients together, add moderate water into mix-
ture and grind them for half an hour to form a homogeneous slurry. Then
pour the slurry onto copper foil and wipe it into thin film with thickness
of 15 μm. After drying under 80 °C for 12 h, the film was cut into slides
with mass loading weight of 1.2–1.5 mg/cm2 for active materials. Then it
was assembled into half cell with lithium plate as counter and reference
electrodes. The whole assembly process was carried out in glove-box filled
with inert gas. The employed electrolyte was a solution of 1.0 M LiPF6 in
the mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC)
with the same volume ratio. The rate capacity and cycling performance
H. Qi et al.
was tested by Neware battery system at the voltage range of 0.05 to 3.00 V.
And CV and EIS were recorded on CHI660 working station.
3. Results and discussion
β-FeOOH adopts monoclinic symmetry with I2/m space group with
connected FeO6 octahedra chains sharing its corners to form a framework
with lots of tunnel structures containing Cl− to form FeO1-xOHClx (β-
FeOOH) [23,24]. The crystal structure along b axis is shown in Fig. 1a.
Rietveld XRD of the as-prepared samples of bare FeOOH, FeOOH/rGO
and FeOOH@PEDOT were shown in Figs. 1b, S1 and Table S1. The lattice
parameters of FeOOH@PEDOT are a = 10.5351 Å, b = 3.0341 Å, c =
10.6310 Å and β = 89.469°. The diffraction peaks of FeOOH, FeOOH@
PEDOT and FeOOH/rGO are all attributed to the same phase of β-FeOOH
(JCPDS 75–1594). The background signal of FeOOH@PEDOT around 30°
slightly rises, which is attributed to the existence of PEDOT. After the addi-
tion of PEDOT, the sample transformed from yellow to black from the insets
of Fig. 1b. The existence of PEDOT is further confirmed by FTIR spectra
displayed in Fig. 1c. The adsorption bands around 1049–1091 cm−1 is re-
lated to vibration of CS. The peaks at 1200 and 1340 cm−1 are attributed
to vibration of C-O-C and CC. These are characteristic absorption peaks
for PEDOT, which could be only found in FeOOH@PEDOT composites. In
addition, the peaks centered at 632 and 857 cm −1 could be assigned to
stretching and bending vibration of FeO bonds [12,21]. The bands around
1630 and 3420 cm−1 are corresponding to OH adsorption in FeOOH
[20,21].
As shown in Fig. 2, bare FeOOH, FeOOH@PEDOT and FeOOH/RGO
all exhibit rod-like structures. The length of bare FeOOH ranges from
300–500 nm (Fig. 2a). In contrast, FeOOH rods in FeOOH@PEDOT
and FeOOH/RGO composites grow much shorter with length of
~200 nm (Fig. 2b,c). This suggests the addition of PEDOT and RGO
Fig. 1. (a) Crystal structure of β-FeOOH(FeO1-xOHClx); (b) Rietveld XRD data of FeOOH@PEDOT and (c) FTIR of FeOOH and FeOOH@PEDOT.
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Journal of Electroanalytical Chemistry 882 (2021) 115005
greatly accelerates nucleation rate and slows down growth speed to
form uniform and nanosized rods. From the amplified TEM images
(Fig. 2d and e), FeOOH rods were encapsulated in PEDOT shell with
a thickness of ~10 nm. In addition, PEDOT layer is also found under
the FeOOH rods (Fig. 2d), which could enhance the electron transport
between FeOOH rods. Compared with pure FeOOH, the size of FeOOH
rod in the composites is smaller than that of pure FeOOH. Fig. 2c shows
the morphology of FeOOH/rGO composites. Nanosized FeOOH rods
distribute uniformly on RGO layers. And RGO layers could be distin-
guished obviously in Fig. 2f.
XPS were employed to analyze the chemical states on the surface of
FeOOH@PEDOT composites. From the survey spectra of FeOOH@PEDOT
and FeOOH/RGO composites, Fe, O, C and minor Cl elements could be
found in both samples. Cl− occupies the tunnel structure to stabilize the
crystal structure of β-FeOOH, therefore Cl− could be detected in β-
FeOOH. The atom percentages of Cl− in FeOOH@PEDOT and FeOOH/
RGO are calculated as 2.35% and 2.57%, respectively. S element could be
only detected in FeOOH@PEDOT composites, which comes from thiophene
group in the PEDOT polymers. Fe 2p peak detected in FeOOH@PEDOT is
almost invisible, which reveals that FeOOH rods are completely coated in-
side PEDOT layers because the metal signal is much sensitive in XPS. The
detective depth for X ray could reach to 5 nm on the surface of the samples
for XPS instrument, suggesting the PEDOT shell is thicker than 5 nm. The
high resolution of XPS spectra of C 1 s could be fitted into three peaks,
which could be attributed to CC (284.6 eV), C-O/C-S (286.2 eV) and O-
C=O (288.3 eV) [25–27]. The fraction of CO and CS group in FeOOH@
PEDOT composites is much higher than that in FeOOH/RGO since more
CO and CS functional groups exist in PEDOT polymers [28]. In Fig. 3c, S
2p spectrum is separated into three peaks, S 2p 3/2 at 163.8 eV, S 2p 1/
2 at 164.9 eV and satellite peaks at 168.7 eV, which is assigned to the exis-
tence of C-S-C bonds in PEDOT [21].
H. Qi et al.
Fig. 2. FESEM images of (a) bare FeOOH rods; (b) FeOOH@PEDOT; (c) FeOOH/RGO; TEM and HRTEM images of (d,e) FeOOH@PEDOT and (f) FeOOH/RGO composites.
CV curves of initial three scans for three samples displayed in Fig. S1
and Fig. 4. For the first negative scan, bare FeOOH exhibits a weak peak
around 1.50 V, which is ascribed to the insertion of Li+ to form LixFeOOH
phase [6]. A sharp peak at 0.55 V is also observed in Fig.S1(a), which is re-
lated to the reduction reaction of LixFeOOH to Fe (0) and the formation of
SEI film [12]. For the following anodic scan, the peak at 1.14 V is corre-
sponding to the reverse decomposition of SEI film consisting of transitional
metal. Another broad peak located at 1.64 V indicates the conversion of Fe
(0) to LixFeOOH. It is worthy noted that the intensity of peak located
around 1.50 V of pure FeOOH is obviously lower than that of FeOOH@
PEDOT and FeOOH/rGO, revealing that high conductivity could facilitate
the insertion of Li+ to form LixFeOOH. Another distinct difference among
three samples is the peak intensity.
For bare FeOOH, the peak intensities gradually reduce. And for FeOOH@
PEDOT, the peak intensity gradually increases and for FeOOH/rGO, the peak
intensities of second scan increases firstly and then decreases. This phenom-
enon suggests PEDOT could increase the electrical conductivity and electro-
chemical reactivity of FeOOH. The corresponding charge-discharge curves of
three samples are displayed in Fig. 4b. FeOOH/RGO and FeOOH@PEDOT
composites deliver high initial discharge capacity of 1515 mAh g−1 and
1335 mAh g−1 with initial coulombic efficiency of 82.3% and 80.6%, respec-
tively. In contrast, bare FeOOH shows 1264 mAh g−1 with a low coulombic
efficiency of 73.3%. It is noteworthy that the initial capacity for three sam-
ples is higher than the theoretical capacity of 746.1 mAh g−1, which is attrib-
uted to the surface adsorption of FeOOH, RGO, PEDOT and other carbon
additives contributing the capacity. Besides, charge-discharge curves of
three samples exhibit obvious difference at the initial insertion of Li+
which is related to the initial slope capacity. Three samples show 366 for
FeOOH/RGO, 243 for FeOOH@PEDOT and 162 mAh/g for bare FeOOH.
FeOOH/RGO and FeOOH@PEDOT samples shows higher slope capacity
than bare FeOOH, which is due to fast electron transfer rate promoting
high reactivity. These results agree well with the corresponding CV analysis.
The cycling performance of three samples was compared at the current
density of 0.5 A g−1. FeOOH/RGO shows highest capacity at initial
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Journal of Electroanalytical Chemistry 882 (2021) 115005
10 cycles, for abundant functional groups including -OH, -COOH, and
-C=O groups on the RGO surface adsorb much more Li+ to contribute
extra capacity. Nevertheless, the capacity fades dramatically after 90 cycles.
It can only maintain 726 mAh g−1 with low capacity retention of 58.1%
(compared to the first charge capacity of 1249 mAh g−1). However, al-
though FeOOH@PEDOT could only deliver 1341 mAh g−1 at first dis-
charge, after undergoing a small fluctuation, it can reach to 1220 mAh
g−1 at 270th cycle with high capacity retention of 113.6%. The increased
capacity may be attributed to pulverization, which induced high surface
area with abundant active sites to adsorb Li ion. The coulombic efficiency
FeOOH@PEDOT of the electrode also maintains close to 100%. Bare
FeOOH rods deliver lowest capacity of 374 mAh g−1 owing to low conduc-
tivity and poor structure stability. Fig. 5b shows the rate capacities of
FeOOH, FeOOH/rGO and FeOOH@PEDOT. FeOOH/rGO exhibits highest
capacity among three samples at low current densities. For example,
FeOOH/rGO electrode could deliver 1218, 1119, 1007 and 858 mAh/g at
0.1, 0.2, 0.5 and 1.0 A g−1, respectively.
However, when the current density further increases to 2.0 A g−1, the
rate capacity for FeOOH/RGO sharply decreases to 376 mAh g−1. In con-
trast, FeOOH@PEDOT exhibits more stable rate capacities with steadily en-
hanced current densities (1066 mAh g−1 at 0.1 A g−1, 983 at 0.2, 922 at
0.5, 831 at 1, 738 at 2). Even at 5 A g−1, FeOOH@PEDOT can maintain
558 mAh g−1, 46.2% higher than that of FeOOH/RGO, which is due to
the unique conductive polymer coating structure of FeOOH@PEDOT.
When the current density returns to 0.1 A g−1, FeOOH@PEDOT can still
reach to 1143 mAh g−1, higher than the original 1066 mAh g−1. Therefore,
FeOOH@PEDOT could storage more Li ion at high current densities than
that of FeOOH/RGO.
Charge/discharge profiles of FeOOH/RGO and FeOOH@PEDOT at dif-
ferent cycles compared to find evolution of their storage mechanism. As is
shown in Fig. 5c, the total capacity is divided into two parts according to
storage sites: plateau and slope capacity. The plateau capacity is resulted
from inside part of the particle [29,30]. And slope capacity is attributed
to the surface storage [30,31]. From Fig. 5c and d, it can be concluded
H. Qi et al. Journal of Electroanalytical Chemistry 882 (2021) 115005

Fig. 3. (a) XPS survey spectra of FeOOH@PEDOT and FeOOH/RGO; High-resolution XPS spectrum of (b) Fe 2p; (c) C1s and (d) S 2p.

Fig. 4. CV curves of initial three cycles for (a) FeOOH@PEDOT composites and (b) charge-discharge curves of initial cycle for three samples.

that the plateau capacity of FeOOH/RGO and FeOOH@PEDOT decreases from particle interior decreases. During the cycling process of FeOOH, the
obviously. In contrast, the slope capacity keeps stable and even rises for particles is pulverized into nanopieces with high surface area, leading to
FeOOH@PEDOT. This phenomenon indicates that the capacity coming steadily increasing slope capacity [12]. Although the total capacity of

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H. Qi et al. Journal of Electroanalytical Chemistry 882 (2021) 115005

Fig. 5. Electrochemical performance for FeOOH, FeOOH/RGO and FeOOH@PEDOT composites: (a) Cycling; (b) rate capacity; Charge/Discharge curves of (c) FeOOH/RGO
and (d) FeOOH@PEDOT; (e) Contribution of plateau contribution for FeOOH/RGO and FeOOH@PEDOT composites.

FeOOH/RGO decreases, its slope capacity almost keeps the same. For
FeOOH@PEDOT, the plateau capacity decreases slower than FeOOH/
RGO, but its total capacity steadily rises. Therefore, interestingly the contri-
butions of plateau capacity of FeOOH/RGO and FeOOH@PEDOT keep al-
most same with each other, suggesting two samples have equal
pulverization rate.
In order to further explore the cause of capacity fading for FeOOH/RGO,
electrochemical impedance spectra (EIS) was tested. EIS of three samples
after 1st cycle and 150th cycle was compared in Fig. 6. The charge transfer
resistance (Rct) of FeOOH/RGO is lowest after first cycle, which agrees well
with its highest capacity at initial cycle. However, when tested after cycling
150 times, Rct of FeOOH/RGO rises to 104.2 Ω. In contrast, FeOOH@
PEDOT has the lowest Rct of 69.3 Ω, which may be attributed to PEDOT
shell could confine the pulverized particles in a fixed space and make
them keep good electrical contact. Rct of FeOOH/RGO increased to
104.2 Ω, suggesting cracked FeOOH rods lost compact contact with RGO
layers after long-term cycling. This phenomenon agrees well with the
poor cycling performance of FeOOH/RGO, which shows a sharp decline
after 80 cycles.
To get further understanding effects of PEDOT and RGO layer on the
electrochemical behavior, the microstructure of FeOOH, FeOOH/RGO
and FeOOH@PEDOT electrodes after cycling are observed. Bare FeOOH

6
H. Qi et al.
Fig. 6. EIS of three samples of FeOOH, FeOOH/RGO and FeOOH@PEDOT: (a) after first cycle; (b) after 150th cycle (c) the fitted results of Rct for three samples.
electrodes are pulverized without a rodlike outline due to repeated inser-
tion and extraction of Li+ ion. The FeOOH/RGO electrode show relatively
complete outline, suggesting RGO reduce the pulverization rate to some ex-
tent. The enlarged images show the rods is pulverized into tiny particles
within 5 nm. This phenomenon is common for converse-type electrodes
since conversion reaction(FeOOH +3Li++ 3e− = Fe + Li3OOH) takes
place by breaking and rebuilding chemical bonds thoroughly [13]. This
will cause dramatic pulverization for particles. Actually, pulverized parti-
cles with tiny size could facilitate diffusion of Li+ ion at initial stage,
resulting in a high capacity at first several cycles. However, the continuous
pulverization will finally make the tiny particles lose electrical contact with
RGO, as shown in inset of Fig. 7b. The effective mass reduction of active
particles will lead to distinct capacity fading. For PEDOT layer coated
FeOOH rods, the rodlike profiles could be well-preserved after long cycling.
The PEDOT shell are still tightly coated on the surface of FeOOH rods which
can improve the structure stability. The amplified images also reveal
FeOOH rods after cycling are also refined to nanoparticles with less than
5 nm. In addition, the lattice distance of cycled FeOOH nanoparticles also
Fig. 7. TEM images of three samples of (a) bare FeOOH, (b) FeOOH/RGO and (c) FeOOH@PEDOT after 150 cycles.
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Journal of Electroanalytical Chemistry 882 (2021) 115005
increases along with the insert-extraction of Li+ ions. The lattice distance
of (400) increases from 0.263 to 0.267 nm for FeOOH/RGO (Fig. 7b), and
the lattice space of (101) rises from 0.290 to 0.292 nm for FeOOH@
PEDOT (Fig. 7c). As we speculated from the discharge curves analysis in
Fig. 5, FeOOH@PEDOT and FeOOH/RGO has the same pulverization
rate. Due to the existence of PEDOT shell, the pulverized nanoparticles
were confined into a fixed and firm space to keep closely contact with
each other. Tiny particles (<5 nm) will high conductivity realize high
rate and stable performance.
CV was employed to investigate electrochemical reaction kinetics of
FeOOH@PEDOT and determine whether the reaction is dominated by
pseudocapacitive mechanisms. CV curves with various sweep rates exhibit
similar profiles from 0.1 to 0.8 mV s−1. The CV curves display 2 cathodic
peaks (~1.68 and ~ 0.78 V) and 2 anodic peaks (~1.84 and ~ 2.55 V),
shown in Fig. 8a. As the sweep rate raises, the cathodic and anodic peaks
only have a small shift toward opposite direction, suggesting low
overpotential resulted from fast reaction dynamics of electrode materials.
According to the equation(ln i = b ln v + ln a) [32,33]，b value (the
H. Qi et al.
Fig. 8. (a) CV with different scan rates for FeOOH@PEDOT; (b) fitted linear relationship between ln(peak current) and ln(scan rate); (c) pesudocapacitance contribution to
total storage at the scan rate of 0.5 mV s−1 and (d) contribution ratio of pesudocapacitance to diffussion provided capacity at different san rates from 0.1 to 0.8 mV s−1.
slope of ln i ~ ln v) is calculated to reflect storage mechanism of Li ion. As is
shown in Fig. 8b, b values of four redox peaks reach to 0.83, 0.98, 0.98 and
0.93, respectively. This suggests the electrochemical reaction process is
dominated by capacitive mechanism, which promotes the high-rate storage
capacity for FeOOH@PEDOT electrode. The pseudocapacitive contribution
is further calculated according to formula (i = k1v + k2v1/2) [33,34]. A
high proportion of 88% belonging to the pseudocapacitive contribution is
obtained at 0.5 mV s−1. As the scan rate increases to 0.8 mV s−1, the per-
centage of pseudocapacitive capacity further rises to 91%. The high ratio
of pseudocapacitive capacity is resulted from high surface area of tiny
FeOOH particles and good electrical contact between each particle.
PEDOT polymers confines FeOOH particles into shell to ensure tight con-
tact, which have been evidenced by smaller resistance of charge transfer
for FeOOH@PEDOT after long-term cycling.
4. Conclusion
In summary, conductive PEDOT polymer supported and coated FeOOH
composites (FeOOH@PEDOT) were fabricated by one-pot method.
FeOOH@PEDOT with this unique coating structure exhibits higher capac-
ity and longer cycle life than the composites of FeOOH rods anchoring on
RGO sheets (FeOOH@RGO). This could be attributed that PEDOT coating
has high electrical conductivity and mechanical strength, which could ac-
celerate electronic transfer and confine the pulverized pieces into shell to
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Journal of Electroanalytical Chemistry 882 (2021) 115005
keep good electrical contact. Therefore, FeOOH@PEDOT composites after
pulverization with high conductivity and surface area show
pseudocapacitance dominated reaction mechanism. Therefore, FeOOH@
PEDOT displays 1220 mAh g−1 at 0.5 A g−1 over 270 cycles (113.6% ca-
pacity retention). This work confirms that improving electrical conductivity
of pulverized particles could make best use of pulverization process to real-
ize fast and durable storage for FeOOH anodes. This strategy could be ex-
tended for other conversion-type anode materials.
Declaration of Competing Interest
We declare that we have no financial and personal relationships with
other people or organizations that can inappropriately influence our work,
there is no professional or other personal interest of any nature or kind in
any product, service or company that could be construed as influencing
the review of the manuscript entitled.
Acknowledgments
This work was supported by the National Natural Science Foundation of
China (Grant Nos. 52002305, 52075409). This work was financially sup-
ported by Shaanxi Province Key Research and Development projects (Grant
No. 2020GY-153) and The Youth Innovation Team of Shaanxi Universities.
H. Qi et al.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jelechem.2021.115005.
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